EP0296450A1 - Résines époxy contenant des groupes oxazolidone - Google Patents
Résines époxy contenant des groupes oxazolidone Download PDFInfo
- Publication number
- EP0296450A1 EP0296450A1 EP88109419A EP88109419A EP0296450A1 EP 0296450 A1 EP0296450 A1 EP 0296450A1 EP 88109419 A EP88109419 A EP 88109419A EP 88109419 A EP88109419 A EP 88109419A EP 0296450 A1 EP0296450 A1 EP 0296450A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- diisocyanates
- groups
- diisocyanate
- bisepoxide
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 title claims description 15
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 title claims description 9
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 title description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 150000004714 phosphonium salts Chemical class 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- ZWWKXEXFVYBART-UHFFFAOYSA-N 2,5-diisocyanato-5-methylcyclohexa-1,3-diene Chemical class O=C=NC1(C)CC=C(N=C=O)C=C1 ZWWKXEXFVYBART-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims 1
- WAMBUHSSUGGLJO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WAMBUHSSUGGLJO-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 quaternary ammonium halides Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- SERCPQYXEUPQHB-UHFFFAOYSA-N 5,6-diisocyanato-5-methylcyclohexa-1,3-diene Chemical compound O=C=NC1(C)C=CC=CC1N=C=O SERCPQYXEUPQHB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000428199 Mustelinae Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
Definitions
- the invention relates to a process for the preparation of oligomeric, oxazolidone-containing polyepoxides from bisepoxides and diisocyanates.
- trimerization of the isocyanates should only take place to a small extent.
- EP-OS 113 575 describes the production of powder coatings containing oxazolidone groups and having epoxy groups, which are prepared by reacting diisocyanates with bisepoxides using quaternary ammonium halides as catalysts. The reaction is not always quantitative in the desired sense. In addition, a large amount of catalyst is required, which remains in the resin and can impair storage stability.
- the invention thus relates to a process for the preparation of oligomeric, oxazolidone-containing polyepoxides from bisepoxides and diisocyanates, characterized in that at 140-180 ° C in the presence of a phosphonium salt as catalyst, either bisepoxide ethers with OH groups corresponding to an OH number of at least 2 , with aromatic diisocyanates, which two differently reactive NCO groups in one amount of at least 1/4 of the weight of the diisocyanate, or bisepoxide esters with OH groups corresponding to an OH number of at least 2, with aromatic, aliphatic or cycloaliphatic diisocyanates, preferably those containing differently reactive NCO groups in an amount of at least 1 / 4 of the weight of the diisocyanate, are reacted with one another in a quantitative ratio of NCO group to epoxy groups of 1: 1.4 to 1: 2.5.
- the bisepoxide ethers suitable for the processes according to the invention are diglycidyl ethers of dihydric, aliphatic alcohols having 2 to 4 carbon atoms or dihydric phenols such as bisphenol A or F or sulfonyl or thionyl bisphenol or their core-substituted derivatives, or bisglycidyl esters of dicarboxylic acids such as succinic acid , Adipic acid, azelaic acid, sebacic acid or dimerized fatty acid, ortho-, iso- or terephthalic acid, tetra- or hexahydrophthalic acid or their ring-alkylated derivatives.
- dicarboxylic acids such as succinic acid , Adipic acid, azelaic acid, sebacic acid or dimerized fatty acid, ortho-, iso- or terephthalic acid, tetra- or hexahydrophthalic acid or their ring-alkylated
- Preferred bisepoxides are bisphenol A or F bisglycidyl ether and hexahydrophthalic acid bisglycidyl ester.
- the bisepoxides mentioned have an OH number greater than 2 (> 2).
- the OH groups can have arisen in the preparation of the bisepoxides from diols or dicarboxylic acids with epichlorohydrin or by targeted conversion of OH-group-free bisepoxides with further mono- or polyols, mono- or polycarboxylic acids, or by partial saponification of the epoxide groups of a polyepoxide.
- the OH number of the bisepoxides mentioned can e.g. according to Chimica, Vol. 33, 1979, No. 3, page 84 titrated in addition to epoxy groups or determined from the IR spectrum using a calibration curve.
- aromatic and aliphatic diisocyanates preferably aromatic diisocyanates, can be used.
- aromatic dissocyanates with two differently reactive NCO groups can be used in combination with diepoxide ethers, e.g. o, p-tolylene diisocyanate, diphenylmethane-2,4'-diisocyanate, naphthylene diisocyanate-1,3 alone or as a mixture with one another or as a mixture with other diisocyanates which have two equally reactive NCO groups, e.g. in a mixture with diphenylamethane-4,4'-diisocyanate, o, o-tolylene diisocyanate, naphthylene diisocyanate-1.5.
- the diisocyanates with different reactive NCO groups should make up at least 1/4 of the total weight of the diisocyanates.
- aliphatic diisocyanates such as hexamethylene-1,6-diisocyanate or cycloaliphatic diisocyanates such as isophonone diisocyanate, methylene biscyclohexyl diisocyanate-4,4 'or -2,4' can be used in combination with the bisepoxide esters.
- Diisocyanates containing two differently reactive NCO groups are preferred. They are used in an amount that is at least 1/4 of the total weight of the diisoanates used.
- Isocyanates which contain two differently reactive NCO groups are preferably used.
- the catalysts suitable for the process according to the invention are phosphonium salts of the formula (I) in which R1, R2, R3 and R4 independently of one another are C5-C10-cycloalkyl, C1-C8-alkyl and C6-C10-aryl and X represents C2-C6 carboxylate and halogen such as Fl, Cl, Br and J, which are named, for example, in DE-OS 21 230 157.
- the cyclohexyl, C1-C8-alkyl or phenyl-substituted phosphonium salts are preferred in the form of the chlorides, bromides, iodides or acetates.
- the catalysts are used in amounts of 0.005 to 1.0% by weight, preferably 0.01 to 0.5% by weight, based on bisepoxide.
- the process is carried out at a temperature of 140 to 180 ° C, preferably from 150 to 170 ° C.
- the quantitative ratio in which the bisepoxides are reacted with the diisocyanates is 1.4 to 2.5 epoxy groups per NCO group, preferably 1.6 to 2.2 epoxy groups per NCO group. In any case, reactive epoxy groups remain in the end product, which are available for subsequent reactions or for crosslinking. The smaller the excess of epoxy groups compared to the NCO groups, the higher the molecular weight of the modified epoxy resins and the higher their melt viscosity.
- the polyepoxides containing oxazolidone groups according to the invention can be mixed with other liquid or solid epoxy resins or reactive diluents and cured with the aid of the usual hardeners such as polyamines, acid anhydrides or polyisocyanates, at customary temperatures of 10 to 150 ° C.
- the hardening products show increased tensile strength, elongation at break, impact strength, ball pressure hardness and heat resistance compared to oxazolidone group-free comparison products.
- the amount of bisepoxide resins and catalysts listed in Table I is weighed into a flask with stirrer and gas inlet tube and heated to 160 ° C. under nitrogen.
- the diisocyanate is added dropwise to the melt so quickly that a temperature of about 170 ° C. is maintained, which can be controlled by switching off the heating or by cooling.
- stirring is continued at 160 ° C. until the calculated epoxy value is reached and no reactive NCO can be detected.
- the product obtained is filled hot as a melt. It freezes when it cools down.
- the examples and comparative examples show that the desired oxazolidone epoxy resins can only be obtained when the epoxy resins containing OH groups according to the invention are used in combination with the diisocyanates according to the invention containing unreactively reactive NCO groups with phosphonium salt catalysis at about 160 ° C.
- OH number was determined by titration according to the quotation on page 4).
- X18 bisphenol A bisglycidyl ether, pure. (OH number: 0, epoxy equivalent weight: 172)
- X20 bisphenol A bisglycidyl ether, technical. (OH number: 15, epoxy equivalent weight: 186)
- X100 bis-glycidyl hexahydrophthalate, technical.
- T65 mixture of 65% by weight of o, p-tolylene diisocyanate and 35% by weight of o, o-tolylene diisocyanate
- T100 o, p-tolylene diisocyanate
- MDI diphenylmethane diisocyanate-4,4 ′
- MDI-M mixture of 55% by weight diphenylmethane diisocyanate-4,4 ′ and 45% by weight diphenylmethane diisocyanate-2,4 ′
- IPDI isophorone diisocyanate, pure.
- Catalyst A tetrabutylphosphonium bromide
- Catalyst B benzyl triphenylphosphonium chloride
- Table I Example: 1 2nd 3rd 4th 5 6 7 Comparative example: 1a 1b 1c
- Catalyst A 0.22 0.22 0.22 0.23 0.24 0.24 0.23 0.23 - 0.3
- Catalyst B - - - - - - - - - 0.23 - Diisocyanate: T65 - - - - 57.3 - - - - - - T100 - - - - - 55.6 -
- composition of the mixtures :
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88109419T ATE69825T1 (de) | 1987-06-24 | 1988-06-14 | Oxazolidongruppen enthaltende epoxidharze. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873720759 DE3720759A1 (de) | 1987-06-24 | 1987-06-24 | Oxazolidongruppen enthaltende epoxidharze |
| DE3720759 | 1987-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0296450A1 true EP0296450A1 (fr) | 1988-12-28 |
| EP0296450B1 EP0296450B1 (fr) | 1991-11-27 |
Family
ID=6330137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88109419A Expired - Lifetime EP0296450B1 (fr) | 1987-06-24 | 1988-06-14 | Résines époxy contenant des groupes oxazolidone |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0296450B1 (fr) |
| JP (1) | JPS6420227A (fr) |
| AT (1) | ATE69825T1 (fr) |
| DE (2) | DE3720759A1 (fr) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4007141C1 (fr) * | 1990-03-07 | 1991-04-11 | Felix Boettcher Gmbh & Co, 5000 Koeln, De | |
| EP0478606A4 (en) * | 1989-06-06 | 1992-05-13 | The Dow Chemical Company | Epoxy-terminated polyoxazolidones, process of preparation, and electrical laminates therefrom |
| EP0449072A3 (en) * | 1990-03-22 | 1992-09-16 | Vianova Kunstharz Aktiengesellschaft | Process for the preparation of cationic binders and their application |
| EP0530812A1 (fr) * | 1991-09-05 | 1993-03-10 | Nippon Paint Co., Ltd. | Composition de résine thermodurcissable contenant un composant oxazolidinone polyfonctionnel et un composant polyamine |
| WO1994002524A1 (fr) * | 1992-07-17 | 1994-02-03 | Siemens Aktiengesellschaft | Melange prepolymere de resines epoxy a structures oxazolidinoniques |
| US5496892A (en) * | 1992-07-17 | 1996-03-05 | Siemens Aktiengesellschaft | Oxazolidinone structures-containing prepolymeric epoxy resin mixture |
| US5591813A (en) * | 1993-05-21 | 1997-01-07 | Hitachi Chemical Company, Ltd. | Amide group-containing diisocyanates and amide group-containing epoxy resins |
| EP0970980A4 (fr) * | 1997-03-27 | 2000-06-14 | Mitsubishi Rayon Co | Composition de resine epoxyde pour plastique renforce de fibre de verre, preimpregne et moulage tubulaire produit au moyen de cette composition |
| WO2000034351A1 (fr) * | 1998-12-11 | 2000-06-15 | The Dow Chemical Company | Composition de resine polyoxazolidone adhesive preparee a partir de polyepoxides et de polyisocyanates |
| US6225377B1 (en) | 1992-07-17 | 2001-05-01 | Siemens Aktiengesellschaft | Blending epoxy resin-polyisocyanate-filler mixture and phenolic resin-filler mixture for molding |
| WO2000009581A3 (fr) * | 1998-08-14 | 2001-12-13 | Dow Chemical Co | Agent modifiant la viscosite utilise dans une composition de resine thermodurcissable |
| WO2013003999A1 (fr) * | 2011-07-04 | 2013-01-10 | Dow Global Technologies Llc | Produits d'addition comme durcisseurs dans des systèmes époxydes thermodurcissables |
| WO2015173111A1 (fr) * | 2014-05-12 | 2015-11-19 | Covestro Deutschland Ag | Catalyseurs pour la synthèse de composés d'oxazolidinone |
| RU2574061C2 (ru) * | 2011-07-04 | 2016-02-10 | БЛЮ КЬЮБ АйПи ЭлЭлСи | Аддукты в качестве отвердителей в термоотверждаемых эпоксидных системах |
| CN106459358A (zh) * | 2014-05-12 | 2017-02-22 | 科思创德国股份有限公司 | 用于生产聚噁唑烷酮聚合物化合物的方法 |
| WO2021167874A1 (fr) * | 2020-02-18 | 2021-08-26 | Covestro Llc | Compositions de polyoxazolidinone |
| EP4011927A1 (fr) * | 2020-12-10 | 2022-06-15 | Covestro Deutschland AG | Composition comprenant de l'oxazolidinone à fonction époxy |
| WO2022122606A1 (fr) * | 2020-12-10 | 2022-06-16 | Covestro Deutschland Ag | Composition comprenant un oxazolidinone à fonction époxy |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100227090A1 (en) * | 2007-10-31 | 2010-09-09 | Zeng Kun Liao | Non-sintering isocyanate modified epoxy resin for fusion bonded epoxy applications |
| RU2014107911A (ru) | 2011-08-01 | 2015-09-10 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Виниловая сложноэфирная смола, содержащая оксазолидоновое кольцо, и продукты на ее основе |
| EP3750933A1 (fr) | 2019-06-12 | 2020-12-16 | Covestro Deutschland AG | Procédé de production de polyoxazolidinones à terminaison de groupe d'époxy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2101498A5 (fr) * | 1970-06-22 | 1972-03-31 | Dow Chemical Co | |
| US3721650A (en) * | 1971-03-22 | 1973-03-20 | Alelio G D | Reactive hydroxyalkyl-onium catalysts for synthesis of polyoxazolidones |
| WO1986006734A1 (fr) * | 1985-05-07 | 1986-11-20 | The Dow Chemical Company | Procede de preparation de polyoxazolidone |
-
1987
- 1987-06-24 DE DE19873720759 patent/DE3720759A1/de not_active Withdrawn
-
1988
- 1988-06-14 DE DE8888109419T patent/DE3866439D1/de not_active Expired - Lifetime
- 1988-06-14 AT AT88109419T patent/ATE69825T1/de not_active IP Right Cessation
- 1988-06-14 EP EP88109419A patent/EP0296450B1/fr not_active Expired - Lifetime
- 1988-06-17 JP JP63149259A patent/JPS6420227A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2101498A5 (fr) * | 1970-06-22 | 1972-03-31 | Dow Chemical Co | |
| US3721650A (en) * | 1971-03-22 | 1973-03-20 | Alelio G D | Reactive hydroxyalkyl-onium catalysts for synthesis of polyoxazolidones |
| WO1986006734A1 (fr) * | 1985-05-07 | 1986-11-20 | The Dow Chemical Company | Procede de preparation de polyoxazolidone |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0478606A4 (en) * | 1989-06-06 | 1992-05-13 | The Dow Chemical Company | Epoxy-terminated polyoxazolidones, process of preparation, and electrical laminates therefrom |
| DE4007141C1 (fr) * | 1990-03-07 | 1991-04-11 | Felix Boettcher Gmbh & Co, 5000 Koeln, De | |
| EP0449072A3 (en) * | 1990-03-22 | 1992-09-16 | Vianova Kunstharz Aktiengesellschaft | Process for the preparation of cationic binders and their application |
| EP0530812A1 (fr) * | 1991-09-05 | 1993-03-10 | Nippon Paint Co., Ltd. | Composition de résine thermodurcissable contenant un composant oxazolidinone polyfonctionnel et un composant polyamine |
| US6225377B1 (en) | 1992-07-17 | 2001-05-01 | Siemens Aktiengesellschaft | Blending epoxy resin-polyisocyanate-filler mixture and phenolic resin-filler mixture for molding |
| WO1994002524A1 (fr) * | 1992-07-17 | 1994-02-03 | Siemens Aktiengesellschaft | Melange prepolymere de resines epoxy a structures oxazolidinoniques |
| US5496892A (en) * | 1992-07-17 | 1996-03-05 | Siemens Aktiengesellschaft | Oxazolidinone structures-containing prepolymeric epoxy resin mixture |
| US5591813A (en) * | 1993-05-21 | 1997-01-07 | Hitachi Chemical Company, Ltd. | Amide group-containing diisocyanates and amide group-containing epoxy resins |
| US5625026A (en) * | 1993-05-21 | 1997-04-29 | Hitachi Chemical Company, Ltd. | Amid group-containing diisocyanates and amide group-containing epoxy resins |
| US6670006B1 (en) | 1997-03-27 | 2003-12-30 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition for FRP, prepreg, and tubular molding produced therefrom |
| EP0970980A4 (fr) * | 1997-03-27 | 2000-06-14 | Mitsubishi Rayon Co | Composition de resine epoxyde pour plastique renforce de fibre de verre, preimpregne et moulage tubulaire produit au moyen de cette composition |
| WO2000009581A3 (fr) * | 1998-08-14 | 2001-12-13 | Dow Chemical Co | Agent modifiant la viscosite utilise dans une composition de resine thermodurcissable |
| WO2000034351A1 (fr) * | 1998-12-11 | 2000-06-15 | The Dow Chemical Company | Composition de resine polyoxazolidone adhesive preparee a partir de polyepoxides et de polyisocyanates |
| CN100379781C (zh) * | 1998-12-11 | 2008-04-09 | 陶氏环球技术公司 | 由多环氧化物和多异氰酸酯制得的聚唑烷酮粘合剂树脂组合物 |
| RU2574061C2 (ru) * | 2011-07-04 | 2016-02-10 | БЛЮ КЬЮБ АйПи ЭлЭлСи | Аддукты в качестве отвердителей в термоотверждаемых эпоксидных системах |
| WO2013003999A1 (fr) * | 2011-07-04 | 2013-01-10 | Dow Global Technologies Llc | Produits d'addition comme durcisseurs dans des systèmes époxydes thermodurcissables |
| WO2015173111A1 (fr) * | 2014-05-12 | 2015-11-19 | Covestro Deutschland Ag | Catalyseurs pour la synthèse de composés d'oxazolidinone |
| CN106459358A (zh) * | 2014-05-12 | 2017-02-22 | 科思创德国股份有限公司 | 用于生产聚噁唑烷酮聚合物化合物的方法 |
| CN106459331A (zh) * | 2014-05-12 | 2017-02-22 | 科思创德国股份有限公司 | 用于合成噁唑烷酮化合物的催化剂 |
| CN106459331B (zh) * | 2014-05-12 | 2019-09-13 | 科思创德国股份有限公司 | 用于合成噁唑烷酮化合物的催化剂 |
| CN106459358B (zh) * | 2014-05-12 | 2020-05-15 | 科思创德国股份有限公司 | 用于生产聚噁唑烷酮聚合物化合物的方法 |
| WO2021167874A1 (fr) * | 2020-02-18 | 2021-08-26 | Covestro Llc | Compositions de polyoxazolidinone |
| EP4011927A1 (fr) * | 2020-12-10 | 2022-06-15 | Covestro Deutschland AG | Composition comprenant de l'oxazolidinone à fonction époxy |
| WO2022122606A1 (fr) * | 2020-12-10 | 2022-06-16 | Covestro Deutschland Ag | Composition comprenant un oxazolidinone à fonction époxy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6420227A (en) | 1989-01-24 |
| DE3866439D1 (de) | 1992-01-09 |
| ATE69825T1 (de) | 1991-12-15 |
| DE3720759A1 (de) | 1989-01-05 |
| EP0296450B1 (fr) | 1991-11-27 |
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